Method for making molding material



Patented Mar. 26, 1946 UNITED vSTATES PATENT OFFICE METHOD rFOR MAKING MOLDING MATERIAL Julius J. Trefz, Evanston, and Leonard S.'Shoberg, Glenview, Ill., assignors to Julius F. Trefz, Evanston, Ill., as trustee Application January 19, 1943, Serial No. 472,850

8 Claims. (01.*260-9) This invention relates yto a method or process for producing a powder Yor similar material adapted for Various uses, and also to the improved material itself. Said invention has especial reference to the practice of the aforesaid method or process in an effective and economical manner for 4thev production of the material in question on a highly commercial scale.

More particularly, this invention pertains to a special material, preferably in the form of a powder, that may be used in the manufacture of molded varticles which are produced under the action of heat and pressure, whereby the resulting structure is tough .and hard, and is characterized by its insolubility and infusibility as well as being able to withstand yshock and severe usage. The material resulting from the practice of the method or process which is herein set forth is a phenolic condensation resinous powder, and it is comparatively inexpensive to manufacture due to the factthat the base or raw material which is supplied to the apparatus is a by-product or Waste which inherently contains the elements which are required in carrying out the method or process. After the constituents have been extracted, the residual matter is utilized as the liller for the commercial product without requiring other ller ingredients to be added.

Briey stated, this invention contemplates the extraction of certain of the .self-contained elements which .are inherent in oat-hulls, such for example as .furfuraL sugar, lignin, aldehyde, alcohol, and other constituents, by subjecting the oat-hulls to the infiltration of live steam under pressure whilst the mass of oat-hulls is being agitated in a digester chamber that is preferably closed to the atmosphere so that the reaction will take place under pressure to hasten lthe process. Under 'this treatment, these desired elements or constituents of the oat-hulls are liberated from the agitated mass and when thus freed are in suspension in a fog, mist, or vapor which arises, passes to, and is collected in a communicating chamber where the vapor is charged with phenol, or the like, preferably in solution. The reaction of the phenolic or like treatment causes the suspended elements to gravitate to the bottom or floor of the reaction chamber and Vthence be returned to the digester .or agitator chamber. The elements or constituents acquired through condensation in the reaction chamber .and returned to the dig-ester chamber become re-mixed with the mass which has remained in the digester. This cycle is preferably continued until all the volatiles have been liberated and the desired constituents have been recovered from the oat-hulls. An alkaline or neutralizing agent such as soda, soda-ash, lime, and the like, is mixed with the recovered constituents to eradicate any acidity that may be present, after which the mass, which has been reduced to the form of a Wet mash in the digester, is dumped from ,the apparatus for dehydration and grinding into the desired granular'or comminuted consistency. The neutralization may be performedin the digester by depositing the alkalizing agent therein, or it may be performed in the reaction chamber whilst the phenol is being discharged into the fog, mist or the'like'.

Because `of the inherent porosity of oat-hulls, it has been ascertained in practice that a mass of theseoat-hulls constitutes an excellent base, for

it has been found that they quite readily become thoroughly saturated with the liquid in the digester, .and thus tend to considerably reduce the time element .in the preparation of the molding material by this process.

f T-he method or process of producing the molding powder contemplated .herein is what may be termed a continuous or single-stage operation, and it is preferably performed in an lapparatus such as disclosed in the accompanying drawing. This drawing shows a vertical longitudinal axial viewthrough an apparatus which is to be understood as typical of a structure for the practice of this method or process.

The apparatus illustrated in the drawing, embodies vertical standards l0 provided with bearing bosses Il at their upper portions that are horizontally bored to receivethe hollow trunnions I2 and I3 projecting axially from the respective end `plates I`2a and |3a, which latter, together with a cylindrical wall I4, form a suitable drum. This drum provides a digester that is adapted to be rotated by devices later to be described, and said drum is provided with an `opening l5 in its cylindrical wall I4 through 'which material may be charged or discharged by removal of a closure cap I6 that is clamped in position across said opening to seal the drum.

The drum may be of any desired dimensions proportionate Yto the service required of it, and it is vprovided with a jacket l'l thatv preferably envelops it, whereby the drum and the material therein maybe hea-ted by a suitable medium such as .steam or otherwise. The rotation of the drum is accomplished by extending the end of its trunnion vI3 beyond the bearing boss l l vand providing Aa relatively large gear w-heel I8 on said extended end, which said gear wheel I8 is in mesh with a toothed pinion I9 that is secured to a drive-shaft |9a and actuated through any suitable source of power. As shown, the gear wheel I8 may be formed at the outer end of the trunnion I 3, while the other end of said trunnion may be provided with an annular ange I3b that is suitably secured to the adjacent end of plate I3a of the drum.

A rotatable shaft 20 extends into the drum through but does not contact the inner surface of the hollow trunnion I3, and said shaft 20 is provided along its length inside the drum with a plurality of blades or paddles 2| that project radially from said shaft 20 and of proper length to agitate the material in the bottom of the drum. The outer end of shaft 20 is journaled in a horizontal bearing boss 20a at the upper end of a support or post 20D, and adjacent this bearing boss said shaft has a large gear wheel 22 secured to it that is meshed with and is driven by the toothed pinion I9. The gear wheels I8 and 22 confront each other With their toothed portions facing and with the pinion I9 between them. This arrangement permits the drum and the paddles to rotate in opposed directions, and since the gear wheels |8-22 are preferably of the same dimensions the drum and paddles are moved a the same relative speed.

A suitable feed pipe 23, having a pressure gauge 25 and a control valve 2B, leads from a suitable source of steam supply and it is adapted through a feed pipe 34, is adapted to maintain the chamber at the desired temperature.

The chamber 28 is above the normal level of the material in thedigester and cooperates therewith to function as a reaction chamber in the practice of this invention. Said reaction chamber is preferably mounted on 'the upper portion of the support or post IU in any suitable manner. A portion of the reaction chamber walls embodies a relatively thick plate or casting 29h eX- tending above and below the chute 29e and the opening in which the chute is disposed. This plate 29h has formed in it an annular passage 4U and has a cylindrical stub 2l, which latter projects into the trunnion I2 to afford rigidity when the plate 29h is bolted or otherwise attached to the standard I 0. .A steam feed-pipe 39 is screwed into the lower portion of the plate 29h and discharges steam into the annular passage 40 heated and maintained at the desired temperato discharge the steamunder pressure into the drum. In order Vto admit the steam into the drum,'the lower end of pipe 23 is provided with a laterally disposed hollow sleeve 23a having an insideV diameter vlarger than the diameter of the shaft 2i) to provide an annular or concentric passageway 23h between the shaft 20 and the sleeve 23a, which latter surrounds the shaft within the hollow trunnion I3. The sleeve 23a is stationary, whereas the trunnion revolves thereon, and the inner end of the sleeve discharges into a hollow enlargement cr header 23cwithin the drum so that it surrounds theshaft 2|) and abuts a shoulder 2&0 on the adjacent portion of said shaft 20. Y

` An L-shaped discharge pipe 24, that is provided with a plurality of discharge or egress apertures, has its lateral or vertical radial arm secured in a pendent manner to and communicates with the header 23C, and the other or longer arm of pipe 24 is horizontal and extends along the lower portion of the drum in close proximity to the cylindrical wall I4. The said apertures are disposed in a manner so that the steam or other heated medium will be discharged or injected directly into the body or mass of material that is being agitated bythe blades 2|, thus permitting the steam to thoroughly infiltrate through the oat-hulls or other furfural-bearing Y `material which is being subjected to a digesting. treatment in the drum. Thus it will be seen that the drum, and itsl immediately'associated parts, function in the manner of 'aV digester.

The hollow trunnionr I2 of the digester is in communication with a walled chamber 28 that has an 'inclined bottom 29 that slants downward toward the trunnion and provided with a chute 29a that enters the bore of the trunnion far 'enough to discharge directly into the digester.

The chamber 28 is preferably enveloped ,by a

'jacket 30 that is spaced from the walls of said chamber whereby rsteam Vor other thermal medium, which kmay besupplied to the jacket ture during the operation of the apparatus in practicing the invention contemplated herein.

An outlet 3| leads out of thev upper portion of the reaction chamber 28, and an adjustable pressure control-valve or other suitable device 3|orV is interposed in said outlet whereby the desired pressure may be maintained within the apparatus during the functioning of the latter. K Y

The vapors, fog, mist and the like that are given olf and which issue the material being agitated in the digester drum I4, will carry in suspension the desirable constituents which are self-contained or inherent in the oat-hullsA or other material that is placed in the digester at the start of the method or process, and said vapors, etc., readily pass into the reaction chamber 28 through the hollow trunnion |2`and the chute 29a. Within the reaction chamber 28, the vapors are treated with a reacting agent which is in solutionv and which is preferably sprayed into the central portion of the reaction chamber through the'medium of an atomizer 33 to cause condensation therein. 'Ihe atomizer is located b'elow the plane of the outlet 3|, the solution being fed to the atomizer by a supply pipe 32 from a suitable source under Y pressure and is controlled by a regulator 32a. In practicing the method or process contemplated herein', it is preferred to form the same in the following manner when oat-hulls, ricehulls, and similar furfural-bearing substances are used for the production of the molding powder: Y

The oat-hull, and the like, are placed in the digester I4 and are moistened with sulphuric acid in solution, after which the closure I8 is clamped into position acrossthe opening I5. The rotation of the drum andl paddles are started, and through the medium of the gearing said elements are moved in oppositedirections at approximately the same speed. The agitated furfural-bearing substances are being continuously infiltrated with steam, preferably under pressure, discharged through perforated pipe 24 to Y erate the constituents inherent in said hulls.

These constituents, which leave the agitated hot mass in suspension in a vapor, are furfural, sugar, lignin, aldehyde, and probably certain volatiles, all of which have been released from the hulls through the action of the steam, the pressure and the sulphuric solution. The liberated constituents in the vapor pass from the digester through the hollow trunnion l2 and enter the reaction chamber 28, where the temperature is preferably slightly below the temperature in the digester. Within the reaction chamber, phenol and the like is sprayed by atomizer 33 into the vapor-borne constituents thus causing the latter to condense and fall to the inclined door 29 upon which they will pass out of the reaction chamber and be returned, on chute 28a, to the digester chamber where these constituents are commingled with the residual mass which is continuously undergoing agitation in the presence of.

steam and pressure.

While the vapor-borne constituents are arising in the digester or agitator chamber, any excessive pressure is relieved through the outlet 3| and its regulator 3|a, thereby permitting the vapor to pass into the reaction chamber. During the spraying of the vapor in the reaction chamber, a neutralizing agent, such as soda, soda-ash, or lime-water, is preferably injected into thereaction chamber and into the vapor therein. As a result of the immediate reaction obtained by the sprayed phenol and neutralizing agent, and the constituents of the hulls, there is a phenolic resin created, which, together with the neutralizing agent, returns to the digester where it is mixed with the residual of the hulls by mechanical agitation. The performance of this cycle or stage is continued until all of the desired constituents have been extracted from the oat-hulls and have become mixed with the residue in the digester, so that no filler need be added to the mass since the residual material provides the required liller for the molding powder. The water and steam is drawn off the digester chamber in any suitable manner, and the phenolic resin and ller substance is removed and dehydrated, after which it is ground or milled to the desired size and is ready for irnmediate use Without addition of extraneous material. y

For quantity production of the molding powof 750 pounds of water containing 56 pounds ofsulphuric acid (95%). The steam in the jacket I1 of the digester I4 should be at a temperature of from 300 F. to 400 F., and the steam pressure which is introduced into the mass of material in said digester should be approximately 270 pounds to 280 pounds per square inch, which will tend to raise the temperature of the mass of material being digested to approximately 400 F. to 425 F.

A molding material of the character contemplated herein, may be obtained by mixing equal proportions of phenol and the furfural which has been obtained by a digestive method of production from oat-hulls, and the like. These ingredients are placed in a digester With a quantity of a neutralized commercial residue of thel hulls which has been left from a digestive process, and this mixture is then heated by steam and pressure, after which the mass is cooled,

be neutralized with an :alkaline agent and then ground to a suitable powder, and the latterpthen mixed, either with or without heat, in a mechanical manner with the commercial product known the, like may be made therein Without departing from the Spirit or scope thereof. The aim of the appended claims is to cover all such changes, modifications and equivalents.

What is claimed is:

1. A method of producing a resinous molding material comprising infiltrating steam into a mass of natural material from which furfural may be extracted during agitation of the mass in a digester to liberate a vapor containingfurfural and other constituents in suspension; transferring the said vapor to a closed reaction chamber communieating with the digester; reacting upon the vapor and suspended constituents by an injection of vaporized phenol to produce a phenol-furfural reaction product Which gravitates to the oor of the reaction chamber; returning the gravitated phenol-furfural reaction product to the digester; and re-mixing said phenol-furfural reaction product with the mass remaining in the digester and with a neutralizing agent in sufficient amount as to neutralize said mass.

2. A method of producing a resinous molding material comprising infiltrating steam into a mass of acidied oat-hulls during agitation of the mass in a closed digester to liberate furfural and other constituents in a vapor; transferring the vaporborne constituents to a closed reaction chamber communicating with the digester; reacting upon the vapor-borne constituents by injecting phenol vapor thereinto, thereby precipitating a synthetic resin of the phenol-furfural type; transferring said resin to the digester and there impregnating the residual oat-hulls therewith; and thereafter neutralizing the mass thereby formed with an alkali.

3. The method of making a synthetic resin which comprises digesting a natural furfuralyielding material with steam in the presence of acid, thereby liberating furfural and other volatile substances in the vapor phase, and reacting upon said furfural and other vapors with phenol Vapor in an alkaline environment.

4. The method of making a resinous molding material, which comprises digesting vegetable furfural-yielding material with steam under agitation and pressure in the presence of added mineral acid, thereby liberating volatile compounds comprising furfural, condensing said volatile I compounds from the vapor phase with a phenolic vapor, thereby forming a fluid resin, and impregnating the digested vegetable material with said resin and a neutralizing agent.

5. The method of making a synthetic resin, which comprises digesting natural furfuralyielding material with steam under pressure in the presence of added acid, thereby liberating volatile substances including furfural, and concurrently, reacting, in an alkaline environment, in the vapor phase upon said substances, which have been previously liberated, With phenol vapor, thereby condensing a resin liquid under the conditions of reaction.

6. The method of making al resinous molding material, which comprises agitating natural furfural-yielding vmaterial with' acid, passing steam therethrough under pressure, thereby entraining substances including furfural released from said natural material, and condensing said entrained substances by reaction with a phenolic vapor in the presence of a basic substance.

Y7. The, method of making a resinous molding material, which comprises digesting acidiedpathulls with steam under agitation and pressure, thereby liberating volatile compounds comprising flurfural, condensing said volatile compounds from the vapor -phase with a phenolic Vapor, thereby forminga fluid resin, impregnating the residual oat-hull material with said resin, and neutralizing said oat-hull material with a basic substance.

8. The method of making a resinous molding material, which comprises agitating oat-hulls with acid, passing steam therethrough under pressure, thereby entraining substances including furfural released from said oat-hulls, and condensing said entrained substances by reaction With a phenolic vapor in the presence of an alkaline catalyst.

JULIUS J. TREFZ. LEONARD S. SHOBERG. 

